This study presents a novel electrochemical strategy for the reduction of U(VI) to U(IV) solids using a catalyst composed of atomically dispersed gallium on hollow nitrogen-doped carbon capsules (Ga-Nx-C). The method relies on the presence of secondary metal ions, such as alkaline earth metals, transition metals, lanthanide metals, and actinide metals, which promote the generation of UO2 or bimetallic U(IV)-containing oxides through a two-electron transfer process. The presence of alkali metal ions, however, prevents the formation of U(IV) solids. Mechanistic studies reveal that the strong binding affinity between U(IV) and certain secondary metal ions suppresses re-oxidation of U(IV) to U(VI), leading to the formation of U(IV)O2 and bimetallic oxides. This work provides fundamental insights into the electrochemical behavior of uranium in aqueous media and offers a promising approach for uranium recovery from nuclear waste and contaminated water. The developed method is applicable for uranium extraction from nuclear waste, contaminated water, and seawater. The study also demonstrates the effectiveness of the Ga-Nx-C catalyst in electrochemical uranium extraction, achieving high removal efficiencies and producing stable U(IV) solids under various conditions. The results highlight the potential of electrochemical methods for uranium recovery and environmental remediation.This study presents a novel electrochemical strategy for the reduction of U(VI) to U(IV) solids using a catalyst composed of atomically dispersed gallium on hollow nitrogen-doped carbon capsules (Ga-Nx-C). The method relies on the presence of secondary metal ions, such as alkaline earth metals, transition metals, lanthanide metals, and actinide metals, which promote the generation of UO2 or bimetallic U(IV)-containing oxides through a two-electron transfer process. The presence of alkali metal ions, however, prevents the formation of U(IV) solids. Mechanistic studies reveal that the strong binding affinity between U(IV) and certain secondary metal ions suppresses re-oxidation of U(IV) to U(VI), leading to the formation of U(IV)O2 and bimetallic oxides. This work provides fundamental insights into the electrochemical behavior of uranium in aqueous media and offers a promising approach for uranium recovery from nuclear waste and contaminated water. The developed method is applicable for uranium extraction from nuclear waste, contaminated water, and seawater. The study also demonstrates the effectiveness of the Ga-Nx-C catalyst in electrochemical uranium extraction, achieving high removal efficiencies and producing stable U(IV) solids under various conditions. The results highlight the potential of electrochemical methods for uranium recovery and environmental remediation.